Skip to content

Research at St Andrews

Phase distribution, composition and disorder in Y2(Hf,Sn)2O7 ceramics: insights from solid-state NMR spectroscopy and first-principles calculations

Research output: Contribution to journalArticlepeer-review

DOI

Standard

Phase distribution, composition and disorder in Y2(Hf,Sn)2O7 ceramics : insights from solid-state NMR spectroscopy and first-principles calculations. / Moran, Robert F.; Fernandes, Arantxa; Dawson, Daniel McLean; Sneddon, Scott; Gandy, Amy S.; Reeves-McLaren, Nik; Whittle, Karl R.; Ashbrook, Sharon E.

In: Journal of Physical Chemistry C, Vol. 124, No. 31, 09.07.2020, p. 17073–17084.

Research output: Contribution to journalArticlepeer-review

Harvard

Moran, RF, Fernandes, A, Dawson, DM, Sneddon, S, Gandy, AS, Reeves-McLaren, N, Whittle, KR & Ashbrook, SE 2020, 'Phase distribution, composition and disorder in Y2(Hf,Sn)2O7 ceramics: insights from solid-state NMR spectroscopy and first-principles calculations', Journal of Physical Chemistry C, vol. 124, no. 31, pp. 17073–17084. https://doi.org/10.1021/acs.jpcc.0c04542

APA

Moran, R. F., Fernandes, A., Dawson, D. M., Sneddon, S., Gandy, A. S., Reeves-McLaren, N., Whittle, K. R., & Ashbrook, S. E. (2020). Phase distribution, composition and disorder in Y2(Hf,Sn)2O7 ceramics: insights from solid-state NMR spectroscopy and first-principles calculations. Journal of Physical Chemistry C, 124(31), 17073–17084. https://doi.org/10.1021/acs.jpcc.0c04542

Vancouver

Moran RF, Fernandes A, Dawson DM, Sneddon S, Gandy AS, Reeves-McLaren N et al. Phase distribution, composition and disorder in Y2(Hf,Sn)2O7 ceramics: insights from solid-state NMR spectroscopy and first-principles calculations. Journal of Physical Chemistry C. 2020 Jul 9;124(31):17073–17084. https://doi.org/10.1021/acs.jpcc.0c04542

Author

Moran, Robert F. ; Fernandes, Arantxa ; Dawson, Daniel McLean ; Sneddon, Scott ; Gandy, Amy S. ; Reeves-McLaren, Nik ; Whittle, Karl R. ; Ashbrook, Sharon E. / Phase distribution, composition and disorder in Y2(Hf,Sn)2O7 ceramics : insights from solid-state NMR spectroscopy and first-principles calculations. In: Journal of Physical Chemistry C. 2020 ; Vol. 124, No. 31. pp. 17073–17084.

Bibtex - Download

@article{5d6ac698ab174efdaa90ecf705d15496,
title = "Phase distribution, composition and disorder in Y2(Hf,Sn)2O7 ceramics: insights from solid-state NMR spectroscopy and first-principles calculations",
abstract = "A NMR crystallographic approach, combining 89Y, 119Sn and 17O NMR spectroscopy with X-ray diffraction and first-principles calculations has been used investigate the number and type of phases present, and the local structure and disorder in Y2Hf2–xSnxO7 ceramics. Although a phase change is predicted with increasing Hf content, NMR spectra clearly show the presence of a significant two-phase region, with a Sn-rich pyrochlore and relatively Hf-rich defect fluorite phase co-existing for much of the compositional series. A single-phase pyrochlore is found only for the Sn end member, and a single defect fluorite phase only for x = 0 to 0.2. A solid-solution limit of ~10% is seen for the substitution of Hf into Y2Sn2O7, although no evidence is seen for any cation ordering or antisite disorder in this phase. In the defect fluorite phase there is preferential ordering of oxygen vacancies around Sn, which is only ever seen in a six-coordinate environment. The remaining vacancies are more likely to be associated with Hf than with Y, although this distinction is less apparent at higher Sn concentrations. To acquire 17O NMR spectra samples were post-synthetically exchanged with 17O2(g), although high temperatures (> 900 ºC) were required to ensure uniform enrichment of different chemical species. although these 17O NMR spectra confirm the formation of mixed-metal materials and the presence of two phases, more quantitative analysis is hindered by the overlap of signals from pyrochlore and defect fluorite phases. In all cases, DFT calculations play a vital role in the interpretation and assignment of the NMR spectra, and in understanding the local structure and disorder in these complex multi-phase materials.",
author = "Moran, {Robert F.} and Arantxa Fernandes and Dawson, {Daniel McLean} and Scott Sneddon and Gandy, {Amy S.} and Nik Reeves-McLaren and Whittle, {Karl R.} and Ashbrook, {Sharon E.}",
note = "The authors would like to thank the ERC (EU FP7 Consolidator Grant 614290 “{\textquoteleft}EXONMR{\textquoteright}”), and EPSRC for support for SS and ASG (EP/L005581/1). SEA would like to thank the Royal Society and Wolfson Foundation for a merit award. We acknowledge support from the Collaborative Computational Project on NMR Crystallography CCP-NC funded by EPSRC (EP/M022501/1).",
year = "2020",
month = jul,
day = "9",
doi = "10.1021/acs.jpcc.0c04542",
language = "English",
volume = "124",
pages = "17073–17084",
journal = "Journal of Physical Chemistry C",
issn = "1932-7447",
publisher = "AMER CHEMICAL SOC",
number = "31",

}

RIS (suitable for import to EndNote) - Download

TY - JOUR

T1 - Phase distribution, composition and disorder in Y2(Hf,Sn)2O7 ceramics

T2 - insights from solid-state NMR spectroscopy and first-principles calculations

AU - Moran, Robert F.

AU - Fernandes, Arantxa

AU - Dawson, Daniel McLean

AU - Sneddon, Scott

AU - Gandy, Amy S.

AU - Reeves-McLaren, Nik

AU - Whittle, Karl R.

AU - Ashbrook, Sharon E.

N1 - The authors would like to thank the ERC (EU FP7 Consolidator Grant 614290 “‘EXONMR’”), and EPSRC for support for SS and ASG (EP/L005581/1). SEA would like to thank the Royal Society and Wolfson Foundation for a merit award. We acknowledge support from the Collaborative Computational Project on NMR Crystallography CCP-NC funded by EPSRC (EP/M022501/1).

PY - 2020/7/9

Y1 - 2020/7/9

N2 - A NMR crystallographic approach, combining 89Y, 119Sn and 17O NMR spectroscopy with X-ray diffraction and first-principles calculations has been used investigate the number and type of phases present, and the local structure and disorder in Y2Hf2–xSnxO7 ceramics. Although a phase change is predicted with increasing Hf content, NMR spectra clearly show the presence of a significant two-phase region, with a Sn-rich pyrochlore and relatively Hf-rich defect fluorite phase co-existing for much of the compositional series. A single-phase pyrochlore is found only for the Sn end member, and a single defect fluorite phase only for x = 0 to 0.2. A solid-solution limit of ~10% is seen for the substitution of Hf into Y2Sn2O7, although no evidence is seen for any cation ordering or antisite disorder in this phase. In the defect fluorite phase there is preferential ordering of oxygen vacancies around Sn, which is only ever seen in a six-coordinate environment. The remaining vacancies are more likely to be associated with Hf than with Y, although this distinction is less apparent at higher Sn concentrations. To acquire 17O NMR spectra samples were post-synthetically exchanged with 17O2(g), although high temperatures (> 900 ºC) were required to ensure uniform enrichment of different chemical species. although these 17O NMR spectra confirm the formation of mixed-metal materials and the presence of two phases, more quantitative analysis is hindered by the overlap of signals from pyrochlore and defect fluorite phases. In all cases, DFT calculations play a vital role in the interpretation and assignment of the NMR spectra, and in understanding the local structure and disorder in these complex multi-phase materials.

AB - A NMR crystallographic approach, combining 89Y, 119Sn and 17O NMR spectroscopy with X-ray diffraction and first-principles calculations has been used investigate the number and type of phases present, and the local structure and disorder in Y2Hf2–xSnxO7 ceramics. Although a phase change is predicted with increasing Hf content, NMR spectra clearly show the presence of a significant two-phase region, with a Sn-rich pyrochlore and relatively Hf-rich defect fluorite phase co-existing for much of the compositional series. A single-phase pyrochlore is found only for the Sn end member, and a single defect fluorite phase only for x = 0 to 0.2. A solid-solution limit of ~10% is seen for the substitution of Hf into Y2Sn2O7, although no evidence is seen for any cation ordering or antisite disorder in this phase. In the defect fluorite phase there is preferential ordering of oxygen vacancies around Sn, which is only ever seen in a six-coordinate environment. The remaining vacancies are more likely to be associated with Hf than with Y, although this distinction is less apparent at higher Sn concentrations. To acquire 17O NMR spectra samples were post-synthetically exchanged with 17O2(g), although high temperatures (> 900 ºC) were required to ensure uniform enrichment of different chemical species. although these 17O NMR spectra confirm the formation of mixed-metal materials and the presence of two phases, more quantitative analysis is hindered by the overlap of signals from pyrochlore and defect fluorite phases. In all cases, DFT calculations play a vital role in the interpretation and assignment of the NMR spectra, and in understanding the local structure and disorder in these complex multi-phase materials.

U2 - 10.1021/acs.jpcc.0c04542

DO - 10.1021/acs.jpcc.0c04542

M3 - Article

VL - 124

SP - 17073

EP - 17084

JO - Journal of Physical Chemistry C

JF - Journal of Physical Chemistry C

SN - 1932-7447

IS - 31

ER -

Related by author

  1. Exploring cation disorder in mixed-metal pyrochlore ceramics using 17O NMR spectroscopy and first-principles calculations

    Fernandes, A., Moran, R. F., McKay, D., Griffiths, B., Herlihy, A., Whittle, K. R., Dawson, D. M. & Ashbrook, S. E., 15 Feb 2021, In: Magnetic Resonance in Chemistry. Early View, 14 p.

    Research output: Contribution to journalArticlepeer-review

  2. Single-step synthesis and interface tuning of core–shell metal–organic framework nanoparticles

    Orr, K. W. P., Collins, S. M., Reynolds, E. M., Nightingale, F., Boström, H. L. B., Cassidy, S. J., Dawson, D. M., Ashbrook, S. E., Magdysyuk, O. V., Midgley, P., Goodwin, A. L. & Yeung, H. H-M., 9 Feb 2021, In: Chemical Science. Advance Article, 9 p.

    Research output: Contribution to journalArticlepeer-review

  3. Thermal dehydrofluorination of GaPO-34 revealed by NMR crystallography

    Dawson, D. M., Macfarlane, L. E., Amri, M., Walton, R. I. & Ashbrook, S. E., 24 Jan 2021, In: Journal of Physical Chemistry C. Articles ASAP

    Research output: Contribution to journalArticlepeer-review

  4. Synthesis of chiral MOF-74 frameworks by post-synthetic modification using an amino acid

    Tanase, S., Gheorghe, A., Dubbeldam, D., Strudwick, B., Woutersen, S., Ashbrook, S. E. & Dawson, D. M., 20 Oct 2020, In: Chemistry - A European Journal. Early View, 10 p.

    Research output: Contribution to journalArticlepeer-review

  5. Site-specific iron substitution in STA-28, a large pore aluminophosphate zeotype prepared using 1,10-phenanthrolines as framework-bound templates

    Watts, A. E., Lozinska, M. M., Slawin, A. M. Z., Mayoral, A., Dawson, D. M., Ashbrook, S. E., Bode, B. E., Dugulan, I., Shannon, M., Cox, P., Turrina, A. & Wright, P. A., 17 Aug 2020, In: Angewandte Chemie International Edition. 59, 35, p. 15186-15190 5 p.

    Research output: Contribution to journalArticlepeer-review

Related by journal

  1. Thermal dehydrofluorination of GaPO-34 revealed by NMR crystallography

    Dawson, D. M., Macfarlane, L. E., Amri, M., Walton, R. I. & Ashbrook, S. E., 24 Jan 2021, In: Journal of Physical Chemistry C. Articles ASAP

    Research output: Contribution to journalArticlepeer-review

  2. Electron-induced modification of self-assembled monolayers of aromatic carboxylic acids

    Asyuda, A., de la Morena, R. O., Sauter, E., Turner, K., McDonald, K., Buck, M. & Zharnikov, M., 12 Nov 2020, In: Journal of Physical Chemistry C. 124, 45, p. 25107-25120 14 p.

    Research output: Contribution to journalArticlepeer-review

  3. Oligomerization of proline catalyzed by Ni on a Au(111) surface

    Seljamae-Green, R. T., Robinson, T., Fruchtl, H. A. & Baddeley, C. J., 18 Apr 2019, In: Journal of Physical Chemistry C. 123, 15, p. 9935-9943

    Research output: Contribution to journalArticlepeer-review

  4. Phonon-glass and heterogeneous electrical transport in A-site-deficient SrTiO3

    Popuri, S. R., Decourt, R., McNulty, J. A., Pollet, M., Fortes, A. D., Morrison, F. D., Senn, M. S. & Bos, J. W. G., 7 Mar 2019, In: Journal of Physical Chemistry C. 123, 9, p. 5198-5208 11 p.

    Research output: Contribution to journalArticlepeer-review

ID: 268896916

Top